Ind. Eng. Chem. Res.

1990,29,931-942 93 1

Development of Catalytic Cracking Technology. A Lesson in Chemical

Reactor Design
Amos A. Avidan*
Mobil Research and Development Corporation, Paulsboro Research Labortory, Paulsboro, New Jersey 08066
Reuel Shinnar*
Department of Chemical Engineering, The City College of New York, New York, New York 10031

Catalytic cracking converts heavy petroleum fractions into gasoline, distillates, and light olefins.
It revolutionized refining over 50 years ago and has been evolving continuously since. Catalytic
cracking was commercialized in fixed, moving, and fluid-bed reactors (fluid catalytic cracking, FCC,
has created fine powder fluidization). The design aspects of this important process, in three major
reactor types, constitute a fascinating lesson in reaction engineering. We examined the properties
of catalytic cracking, its chemistry, kinetics, and thermodynamics, and their influence on design.
Of the hundreds of complex reactions, catalytic and thermal, it is the conversion of hydrocarbon
t o coke and gas that dominates reactor and regenerator designs. The effects of hydrodynamics on
cracking are examined through the concept of contact time distribution, and the discussion of the
various reactor and regenerator types concludes with a summary of process control.

1. Introduction Table I. Thermodynamics of Cracking Reactions (at 800 9)

We are honored to participate in an issue dedicated to
Hugh Hulburt. Hugh was a dear friend, and one of his
great contributions to the profession was his editorship of
the monthly, Industrial & Engineering Chemistry Process
Design and Development. I&EC has published some of
the most significant contributions to the understanding
of catalytic cracking over the years, as can be judged from
our references. Hugh had a deep understanding for the
need to encourage publications that deal with the design
process in a rigorous, academic way, and in this paper we
analyze the development of catalytic cracking from a re-
action engineering point of view.
Catalytic cracking has been one of the key processes in
petroleum refining for over 50 years. Modern fluidized
solids technology has its origin in the development of fluid
catalytic cracking (FCC) in the 19409. Catalytic cracking
has evolved significantly in the past 50 years but has not
reached the status of a mature technology. It was first
commercialized in fixed-bed reactors using salt bath heat
exchangers. The moving bed reactor, a widely used tech-
nology today, is derived from thermofor catalytic cracking
(TCC) a moving bed catalytic cracker. However, today
FCC has gained prominence (over 350 commercial units
worldwide, with a capacity of over 1.6 X los m3/day).
The history of the development and commercialization
of catalytic cracking was reconstructed in detail in a recent
review (Avidan et al., 1990). In this paper, we will analyze
the development of catalytic cracking from the point of
view of today’s reaction engineer. We want to show how
the properties of catalytic cracking, and available tech-
nology, determined its development.
2. Chemistry of Catalytic Cracking
kcal/mol
reaction AH AG
2 17 -9
3 12 -14
4 (n = 2) -12 14
5 18 -43
6 -15 -76
different process parameters. The level and detail of the
required knowledge about process chemistry depend on
the purpose. Developing and testing new catalysts requires
a more detailed knowledge than is needed for the design
of reactors. We will limit ourselves here with reactor de-
sign.
Consider the cracking of a high molecular weight pa-
raffin to a lower paraffin and an olefin:
CnH2n+2 CmH2m+2 + Cn-m&(n-m)
+ (1)
for example,
-
C20H42 ClOH22 + ClOH20
Cracking is endothermic (thermodynamic properties are
(2)
given in Table I), a feature that has an important influence
on reactor design. Naphthenes undergo similar reactions,
while aromatic compounds can undergo side-chain split-
ting, yielding an olefin and an aromatic. Multiring aro-
matics normally do not crack but can undergo trans-
alkylation and side-chain splitting reactions. The increase
in the number of moles in cracking and equilibrium is
favored by low pressure. However, conversion is con-
strained by kinetics and not by thermodynamics.
There are several competing reactions to the type shown
in eq 1. Paraffins and olefins formed can crack further
by the same mechanism. Olefins can crack by a reaction

-
The first, and one of the most important, part of a re- such as
actor design is the understanding of process chemistry.
The complex processes that occur on a catalytic surface C10H20 2C5H10 (3)

-
during the cracking process are poorly understood. How- Olefins can also polymerize
ever, for a reaction engineer, understanding the chemistry
has a very specific meaning, and Hugh Hulburt was one n-C5H10 C5nH10n (4)
of the first to clearly define it. What is needed is an
understanding of the overall reactions, their thermody-
namics, and the way overall reaction rates are affected by -
and can also undergo hydrogen-transfer reactions such as
C1oH2o CTH8 + C& + 2H2 (5)

* Correspondence can be addressed to either author.

or
-
CloH2o CYHs + 3CH4 (6)

0888-5885/90/2629-0931$02.50/0 0 1990 American Chemical Society

932 Ind. Eng. Chem. Res.*Vol. 29, No. 6, 1990
t
Gibbs 0
__
60 I I I 2
0 200 400 600 800
Temperature, "C
Figure 1. Effect of temperature on Gibbs free energy of cracking
for a model compound.
Olefinic polymers and other high molecular weight
compounds with low hydrogen content, plus low molecular
weight gases such as CHI and H2, are formed. Some of
these higher molecular weight compounds form "coke".
Overall, one can write
C,H,, -
cake f gas (7)
It is this reaction that dominates the design of catalytic
cracking reactors.
One important question in reactor design is the tem-
perature range that minimizes thermodynamic constraints
on conversion or the range of the desirable reaction AG,
which is significantly negative (preferably less than -5
kcal/mol). There is a large number of individual com-
pounds involved in catalytic cracking, but some conclusions
can be drawn from model compounds. Cracking reactions
are endothermic, but as the AH is significantly larger than
the AG, AG decreases with increasing cracking tempera-
ture. For one model compound (Figure l),AG is -5.0 at
300 "C. Generally, the lower the molecular weight of a
compound, the higher is the temperature required to crack
it. Thermodynamics thus restricts the lowest temperature
for cracking for any catalyst to approximately 300-400 "C.
3. Kinetics of the Cracking Reactor
Cracking is a complex process since there are thousands
of individual compounds in the feed and in the products.
Fundamental kinetic modeling, following all compounds,
has not been performed as of yet and may be unnecessary.
Many of the species present can be lumped into groups.
The more lumps, the more difficult is the mathematical
treatment and the more accurate is the description of the
system that is needed (including feed analysis). Weekman
(1969) has shown that, for reactor design purposes, a simple
three-lump model is sufficient, as it contains the salient
feed -
features of the system important for the designer:
kt
gasoline (8)
\ / .
coke + gas
Reactions 1 and 2 are pseudo second order (second order
in mole fraction but not in partial pressure), whereas re-
action 3 is pseudo zero order in mole fraction and therefore
independent of conversion. Reaction rates depend on the
catalyst used, operating conditions, and feed properties.
All three reaction rates are affected by catalyst deactiva-
tion, which has a permanent component and a regenerable
part (due to coking). One can write for atl three reactions
kj = k 10. t cn-1 (9)
where Iz,, is the catalyst activity for the regenerated cat-
alyst, n varies from 0.4 to 0.6 for silica-alumina catalysts
(n is lower for zeolites), and t , is the average residence time
of catalyst in the hydrocarbon environment.
Yield Vol% Yield. Wt% 5
€4 70 80 90 1W €4 70 80 90 1W
Con"err!on,VIllS Canversion. VoI%
1 Amorphous Catalyst
Zeolhe Catalyst
Figure 2. Gasoline and coke yields vs conversion for zeolite (on
silica-alumina support matrix) and silica-alumina (amorphous)
catalysts (based on FCC kinetic model (Jacob et al., 1976)).
For coke formation, this results in the Voorhies (1945)
equation:
C, = At," (10)
The exponent n = 0.5 was related by Voorhies to a diffu-
sion mechanism of coke precursors through a coke layer.
In differential form, eq 10 is
dC,/dt, = nAt,"-l (11)
The average catalyst residence time, t , is simply related
to the space velocity and the catalyst to oil (C/O) ratio by
Combining the principles of Voorhies (1945) and Blanding
(1953), Weekman and Nace (1970) represented cracking
as an apparent second-order reaction:
dX/dt, = k,Q,(100 - X)' (13)
where X is conversion, typically defined as 100 - volu-
metric yields of products boiling higher than gasoline (220
"C). Note that this "conversion" is really a selectivity.
Cracking is a high conversion process in the sense that
almost every molecule in the feed undergoes some change,
but conversion as used here is typically 70-80 vol %.
Q, is a catalyst decay function. Two forms of Q, can
represent cracking data: a first-order decay (exponential)
and an nth power decay similar to eq 9. In addition, it is
assumed that the cracking activity declines in proportion
to the coking activity. Furthermore, Weekman and Nace
assumed that the decay function for gasoline cracking (k2)
is of the same shape as eq 13 with the same but with a
different rate constant. Many more complex mechanisms
have been proposed, but the mechanism of eq 8 is suffi-
cient to illustrate basic principles. One of the most useful
lumped models published, and the one we use here too,
is the one published by Jacob et al. (1976).
A ratio of coke yield to normalized conversion (or
"crackability") has been used for many years to analyze
cracking data:
k , = coke yield/crackability = C(lO0 - X ) / X (14)
The typical gasoline yield over zeolite and Si/Al catalysts
in gas oil cracking is shown in Figure 2A as a function of
conversion. The gasoline yield increases with conversion
up to a maximum and then decreases as reaction 2 in eq
8 predominates, and gasoline cracks to lighter products and
to coke (coke yield is shown in Figure 2B).
4. Cracking Catalyst Deactivation by Coke
Presently known cracking catalysts deactivate quickly
by coke deposition. Some coke is formed by polymeriza-
tion and condensation of primary cracking products. Coke

I_\ \ i
A. HIC Ratio as Function of 1.Hexane 6 : HIC Ratio in Combusted or
Conversion (Adapted from Wolciechowski and Stripped Coke
Coma, 1986)
Ratio
HIC
Aiomic HIC
Atomic
Ratio
0 500
1 0 z a 3 0 4 0 ~
1-Hexane Convenlon pi%) Stripping or Combustion Time
Figure 3. H/C ratio in coke.
10000 r
Cracking
1000 I
Catalyst 100 - Coke,
Activity
Silica-Alumina
1 -
0 1
Coke Content on Catalyst, %
Figure 4. Cracking catalyst activity vs coke content.
is not a clearly defined compound but a complex mixture
of hydrocarbons. Coke also contains sulfur and nitrogen
compounds, which are the source of SO, and NO, emis-
sions in the regenerator flue gas. While it is often assumed
that coke is mostly carbon, in the form of combined aro-
matic rings, other compounds are also present. A con-
siderable fraction of the coke is easily strippable by steam,
or other gases, at typical reaction temperatures (540 OC).
At higher temperatures, gasification by steam may also
occur. The history of catalytic cracking has been domi-
nated by the competition between cracking and coking.
Some fraction of the coke deposited on spent cracking
catalyst comes directly from unconverted feed molecules.
These can include complex structures such as asphaltenes.
A large fraction of the Conradson carbon residue (CCR)
in the feed is incorporated into coke. The typical H/C
atomic ratio of coke for one model compound (1-hexene)
is shown in Figure 3A for a common cracking catalyst, a
Y zeolite. The initial coke formed has a H/C ratio of 2,
a ratio close to the H/C ratio in the feed and the major
product-gasoline and olefinic hydrocarbons. As conver-
sion increases, the coke becomes more aromatic. The high
H/C %eke" is the first to be removed by stripping or by
combustion (Figure 3B). The more “graphitic”,
‘condensed”, or “residual” carbon is removed last, at a
slower rate. High-efficiency combustors can reduce re-
sidual carbon on regenerated catalysts down to less than
0.05 w t %.
The cracking activity decreases with the coke content
of the catalyst. A typical plot for pure zeolite and an
amorphous silica-alumina catalyst is given in Figure 4.
During burnoff, the coke is redistributed, and residual
coke, while reducing activity, has a lower impact as com-
pared to fresh coke. For comparison, the activity of a
reforming catalyst as a function of coke content is shown
in Figure 5. The effect of coke on activity is much smaller
in reforming, and the catalyst can have a much higher coke
content before most activity is lost (20% versus 1% in
catalytic cracking).
Ind. Eng. Chem. Res., Vol. 29, No. 6 , 1990 933
530
520
Temp. ‘C
Required
tor Constant
Conversion
510
0 5 10 15 20
Coke Content on Catalyst, %
Figure 5. Effect of coke content on activity of Pt reforming catalyst.
2
% on 1
Catalyst
Amorphous
Silica-Alumina
2 0
0 10 20 30 40 50
Time on Streams, Sec.
Figure 6. Coke deposition on zeolite and silica-alumina catalysts
as a function of time.
Coking occurs rapidly, and the coking rate is a function
of catalyst properties, feed composition, temperature, and
pressure. For a given temperature, pressure, and feed
composition, the coke level is simply a function of time.
A typical coke-time curve is shown in Figure 6 for silica-
alumina and zeolite catalyst. Comparison of Figure 6 to
Figure 4 shows that zeolite catalyst loses over 90% of its
initial activity after 1s, whereas silica-alumina loses this
amount of activity in over 1 min. Coking deactivates a
cracking catalyst within a much shorter time period than
in almost any other catalytic process. The catalyst
therefore requires frequent regeneration, and it is this
frequent regeneration that dominates the design. There
is another aspect of catalyst regeneration that dominates
design consideration. As approximately 5 wt 9% of the feed
is converted to coke, it is important that the heat evolved
in combustion be recovered.
The other mechanism of catalyst deactivation is
“permanent” deactivation by dealumination and metal
poisoning. This component of deactivation cannot be
recovered in the cracking reactor-regenerator system.
Dealumination is caused by steaming in the regenerator,
which is proportional to steam partial pressure, regener-
ation temperatures (in an Arrhenius form), and catalyst
activity to a power larger than one. Metal poisoning by
sodium, nickel, and vanadium is more important as heavier
feeds (such as residuum) are processed. Metals buildup
on the catalyst increases coke and gas yields and accel-
erates catalyst deactivation. Catalyst makeup require-
ments in catalytic cracking are determined by the need to
maintain a desired activity level to compensate for these
deactivation mechanisms.
5. Thermal Cracking
Another important competing reaction is thermal
cracking. Thermal cracking was first used for the pro-
duction of gasoline from fuel oil 80 years ago and is still
used today in resid cracking, visbreaking, and coking op-
934 Ind. Eng. Chem. Res., Vol. 29, No. 6, 1990

erations in petroleum refineries. Thermal cracking is less 1.8

selective than catalytic cracking as more methane is formed

and the ratio between reactions 1 and 7 is lower. Thermal 1.6
cracking is undesirable, and the reactor designer must
minimize it. 1.4
The rate of thermal cracking strongly depends on tem-
perature and feed. Below 450 "C the rate of thermal 1.2
cracking is low for most hydrocarbons, while above 600 "C
the rate is fast for all hydrocarbons except methane. Some 1
compounds tend to undergo thermal cracking, forming
coke quite fast above 475 "C. Such compounds are lumped 100 150 200 250 300
together as CCR. The race of thermal cracking increases Gas-Oil Feed Paltlal Pressure, kPa
with molecular weight and therefore with the boiling point. Figure 7. Effect of pressure on coke yield (based on FCC kinetic
On the other hand, thermal cracking may play a positive model (Jacob et al., 1976)).
role in the catalytic cracking of heavy petroleum fractions.
1.5
Very large molecules cannot be catalytically cracked in a I
zeolite catalyst, but fragments and free radicals formed by
thermal cracking can be acted upon. However, for lighter
fractions, thermal reactions are detrimental to product
quality and yield.
To summarize, the main features of catalytic cracking
chemistry are as follows:
(1) The reactions are consecutive, and the desired
products such as gasoline continue to crack to lighter
products and coke.
(2) Coke and low molecular weight gases such as H2 and 480 500 520 540
Temperature, 'C
methane are formed as undesirable parallel products.
(3) Thermal cracking occurs at high temperatures, and Figure 8. Effect of temperature on coke yield (based on FCC kinetic
the feed cannot be preheated above 425 "C. model (Jacob et al., 1976)).
Some cracking of gasoline into lighter gases is not nec-
100
essarily detrimental, as the olefins and isobutane produced Mid-Continent Gas Oil Feed
can be alkylated. The first major use of catalytic cracking
in World War I1 was to produce aviation gasoline, which
was composed of FCC naphtha, alkylate, and tetraethyl-
lead. Increasingly, light olefins today may be valued more Rate
than gasoline for petrochemicals production. Constant
lSec
The development of cracking technology has been dom-
inated by the need to minimize undesirable side reactions
such as thermal cracking and coking while maximizing
yields of desirable products. One way to achieve that is 1 ° T
the continuous search for better catalysts. 10.3
Over the years, development of new catalysts led to 1.0 1.1 1.2 1.3 '4
substantial improvements in the relative rates of cracking 17(IPK x 1 0 3 )
to thermal reactions, increasing gasoline yield. Synthetic Figure 9. Thermal cracking data (Chen and Lucki, 1986).
silica-alumina catalysts followed natural clays, and in the
early 1960s Mobil introduced zeolites that increased re- 7. Effect of Temperature
action rates and selectivity (up to 50% higher gasoline Cracking temperature is one of the main variables that
yield). These developments had a significant effect on unit allow the operator to change yields and product compo-
design. sition. For the designer, three effects are important.
A second way is to develop better reactor designs, and (1) The activation energy of coking is lower than that
it is this way that is our main concern here. To understand of cracking. This effect can be seen in Figure 8 where coke
the choices facing the designer, we will first discuss the yield divided by crackability is plotted as a function of
impact of operating conditions such as pressure, temper- temperature. There is an advantage to operate at higher
ature, and residence time. temperatures, as this reduces the amount of coke forlned
for a desired conversion.
6. Effect of Pressure (2) The limit of the permissible temperature (aside from
Pressure has little effect on the overall thermodynamic metallurgical problems) is due to thermal reactions.
constraints within the range of low pressures used in Thermal cracking by noncatalytic free-radical reactions has
catalytic cracking. Lower hydrocarbon partial pressure a higher activation energy than catalytic cracking and
favors cracking over coking and is therefore desirable. The therefore predominates at high temperature. Thermal
minimum total pressure is determined by the cost of the cracking rate for Mid-Continent gas oil feed is given in
gas plant and is at present above 300 kPa. However, hy- Figure 9 (Chen and Lucki, 1986).
drocarbon partial pressure can be reduced by steam in- (3) Higher temperatures require shorter residence time
jection (typically 1-5 wt % of the feed). Other means to (higher space velocity) to prevent overcracking, and there
reduce partial pressure include the recycle of some light are practical limits to how low they can be reduced to.
hydrocarbon gases, but the cost should be balanced against
the yield benefits. A typical plot of the effect of pressure 8. Residence Times a n d Contact Times
on k, (coke yield divided by crackability) is shown in Figure To reduce thermal cracking, the reaction engineer has
7. another tool-the relative adjustment of contact versus

residence times. When two parallel kinetic reactions are
promoted by the same catalyst, selectivity can be improved
by proper choice of a catalyst. However, if one of the two
reactions is thermal, one can also minimize the actual
residence time, while keeping catalytic conversion constant.
Catalytic conversion is determined at a given temperature
and pressure by the following.
(1) Space Velocity. The space velocity is the hourly
mass flow rate of the feed divided by the total weight of
catalyst in the reactor (WHSV). Decreasing the space
velocity while keeping the residence time constant in-
creases the ratio of catalytic cracking to thermal cracking.
However, there is a limit as to how much catalyst can be
fitted into a given volume. In addition, selectivity suffers
because of increased solids backmixing.
(2) Activity of the Catalyst. The ratio of catalytic to
thermal cracking can be increased by increasing the ac-
tivity of the catalyst. If the ratio of thermal to catalytic
cracking is fixed, then a given catalyst activity per unit
volume results in a maximum permissible temperature and
a maximum permissible residence time. Higher temper-
atures reduce the ratio of catalytic coking rate to catalytic
cracking rate and also improve some product properties,
such as octane.
(3) Uniform Contact Time Distribution. The contact
time distribution (Shinnar et al., 1973; Shinnar, 1986) is
a dimensionless measure of how conversion and product
distribution in the reactor deviate from plug flow. Uniform
contact time improves selectivity.
The concept of a residence time distribution has had a
strong impact on reaction engineering over the past 30
years. But it only applies rigorously to homogeneous re-
actors, as it assumes that all molecules stay in the reactor
the same amount of time regardless of their state. In
heterogeneous systems, molecules are absorbed at a sur-
face, and adsorption and desorption are selective: the real
sojourn times of molecules can be different for different
species. Furthermore, it is not residence time in the reador
that counts but the time in contact with a catalytic surface.
For a first-order reaction, one can define a contact time
distribution rigorously. If we assume a first-order reaction
network with rate matrix Ri, then the outlet composition
in a plug flow reactor is
+
Cj = Ajo CAjnCXnr (15)
where Aj,, are constants determined by the feed compo-
sition, A,, are the eigenvalues of the rate matrix, and 7 is
a time constant related to space velocity. For any iso-
thermal catalytic reactor with arbitrary flows, one can show
in a similar fashion to a homogeneous reactor that outlet
composition is
+
Cj = Ajo CAjn@(Ant) (16)
The funciton $ ( A n t ) is the Laplace transform of the
function W). The contact time distribution is only correct
for the specific pseudo-first-order reaction matrix for which
it was measured. It is a quantitative measure of how the
flow deviates from plug flow.
As molecules are absorbed on a catalyst surface (or in-
side zeolite crystals), the actual sojourn time of a molecule
in the reactor can be much larger than the residence time
in the gas phase. Depending on absorption, the difference
can be an order of magnitude. There is virtually no data
in the literature to account for this effect, which is very
important in a fixed or fixed-fluid bed reactor. On the
other hand, in an entrained-bed reactor such as an FCC
riser, the sojourn time of any molecule is limited to the
residence time of the catalyst particles. (Typically, the
average solids residence time in the FCC reactor is 3 times
Ind. Eng. Chem. Res., Vol. 29, No. 6, 1990 935
Relative
Burning
Rate
1.0 1.1 1.2 1.3
irr (IPKx 103)
Figure 10. Coke burning rate as a function of temperature (based
on Weisz and Goodwin (1963) and Prater et al. (1983)).
35
'"h
25
ResIdence
The,
Minutes
600 650 700 750
Temperature,'
C
Figure 11. Effect of temperature on coke burning rate.
the average gas residence time, or 5-25 s.) Therefore, if
thermal reactions affect molecules absorbed on the Catalyst
surface, then there will be a significant difference between
an entrained bed and a stationary catalyst type of reactor
(such as many laboratory-scale FCC reactors (Sapre and
Leib, 1990)).
The flow pattern can deviate considerably from plug
flow, if catalyst densities vary across the cross section or
if the catalyst phase has significant backmixing due to
clustering. \k(t)an be strongly different from plug flow,
which can lead to yield penalties. A uniform \k(t)also
requires that there would be no diffusional resistances
inside the catalyst particle. This limits the particle size.
9. Kinetics of Coke Combustion
Catalytic cracking yields large amounts of coke (4-8 w t
% of feed). Hydrogen-rich compounds either volatilize at
the temperatures of a typical regenerator (650-800 "C) or
crack to combustible volatiles and coke. The time required
for catalyst regeneration is dominated by the rate of 'slow
coke" combustion. The activation energy of the combus-
tion is approximately 35 kcal/mol. A typical curve of
reaction rate versus temperature is given in Figure 10.
The time required for regenerating a catalyst with 1%
coke (with 1%oxygen breakthrough) is given in Figure 11
as a function of temperature. This time scale is important
as it fixes catalyst inventory and regenerator size.
Reducing the size of the regenerator and the catalyst
inventory are important for two reasons: FCC regenerators
are large and their cost is a significant fraction of total unit
cost. Furthermore, minimizing catalyst inventory has
significant advantages not only in reducing operating costa
but also in allowing faster adjustment of the inventory to
changing needs of feed or product composition.
FCC units operate in "heat balance", and hot catalyst
from the regenerator supplies part of the heat of cracking.
The FCC unit heat balance depends on catalyst activity,
feed properties, feed preheat, and reactor temperature.
The heat balance also depends on the desired C02/C0
ratio in the regenerator flue gas. The products of the
936 Ind. Eng. Chem. Res., Vol. 29, No. 6, 1990
Maximal
Particle
Size, mm
500 550 600 650 700
Regeneration Temp., "C
Figure 12. Maximal particle size to avoid intraparticle temperature
excursion.
primary combustions are CO and C02 and HzO, and the
C02/C0 ratio is a function of temperature. CO reacts with
O2to form C02in a thermal free-radical reaction, but this
reaction is slowed by the presence of solids. If the flue gas
contains excess air, it will ignite as soon as the solids are
removed. Until recently, the design and operation of re-
generators was dominated by this feature. Nowadays,
additives containing precious metals, such as platinum,
allow complete combustion to C02.
The combustion of CO to C02 can also be achieved by
increasing combustion temperatures. As the activation
energy of homogeneous combustion of CO to C02 is high
(approximately 70 kcal/mol), temperatures of above 700
"C will result in complete CO combustion, given sufficient
air, but material and catalyst stability constraints reduce
the maximum temperature below that obtainable from the
heat balance. Catalysts deactivate at high temperatures
by sintering and by steaming. Today's FCC catalysts can
be safely regenerated at temperatures of up to 850 "C
without excessive damage to them by sintering, but
deactivation by steam requires significantly lower tem-
peratures. The designer therefore faces a compromise
between minimizing steam deactivation by lowering tem-
perature and reducing the size of the regenerator by in-
creasing it. Another key to reduce deactivation of steam
is to use two-stage regeneration: the first stage, where
H2-richcoke is burned, is operated at low temperature; the
second stage is operated at a high temperature.
The required residence times for combustion given in
Figure 11were calculated for an isothermal vessel. FCC
regenerators are not always isothermal, and one potential
source for temperature nonuniformity is mass-transfer
limitations inside catalyst particles. The impact of mass
transfer has to be minimized so that the temperature inside
the catalyst particles will not exceed gas-phase tempera-
ture. Diffusion control in combustion is a result of fast
reaction rates. Diffusion times vary with the square of the
diameter of a catalyst particle, whereas reaction rates are
a function of temperature.
Figure 12 shows the relation between the maximum
particle size and temperature. Particle sizes need to be
below 200 Fm so that the regenerator can operate above
650 OC while avoiding high intraparticle temperatures.
The minimal particle size in fixed bed reactors is 1 mm
whereas in the moving bed it is about 3 mm. Only fluid
beds operate with particles below 200 Fm. In processes
that have much lower coke deposition per unit of feed,
there are other ways to protect the catalyst. A common
way is to use dilluted combustion air. This reduces the
adiabatic temperature rise of the air-carbon reaction but
is impractical in FCC due to the large volumes of air in-
volved.
Flue Gas Product
Catalyst
4
7egeneration Cracking
Regenerated
750
Air Feed
Figure 13. Schematic diagram of continuous activity reaction sys-
tem (FCC,TCC).
10. Development of the Cracking Reactor
Having outlined the chemistry of cracking reactions and
the kinetic constraints, let us now examine how different
designs dealt with the challenges. We want to show why
modern FCC technology won over the other designs and
examine the chemical reaction engineering lessions that
can be learned for similar design problems.
Three different types of reactors have been developed
for catalytic cracking. The fixed-bed reactor enjoyed
prominence from 1936 to the early 1940s but is no longer
used today. Only two reactor types are still in use, and
only one, the fluidized bed catalytic cracker (FCC), is used
in new designs. Few operating moving bed reactors (TCCs)
are left today, and they are being gradually replaced by
fluid-bed crackers. But all three designs have had a lasting
impact on chemical reactor design technology.
To understood the underlying reasons for reactor choice,
let us examine the criteria resulting from the kinetic
constraints discussed in the previous sections.
(1) Catalytic Cracking Using a Catalyst That
Deactivates Quickly Due to Coking. In a fixed-bed
reactor, each new element of feed meets a catalyst with
lower activity than the previous element of feed. As con-
version depends on the product of catalyst activity and
space time, this is similar to a reactor with constant cat-
alyst activity but nonuniform contact time. This lowers
conversion and the yield of intermediates in a system of
consecutive reactions.
One way to overcome changing the catalyst activity is
to move the catalyst continuously through separate reac-
tion and regeneration zones (Figure 13). The average
reactivity of the catalyst bed is kept constant by contin-
uously removing coked catalysts from the bed and adding
regenerated catalyst to it. Each catalyst particle still ex-
periences a reaction-regeneration cycle, but the feed sees
constant average catalyst properties.
Two approaches to realize this concept of moving cat-
alyst between reactor and regenerator were developed
simultaneously around 1940. Both used the conceptual
scheme illustrated in Figure 13, and both are still being
used for many other applications today. One used a
moving bed with large catalyst particles; the other used
fluidized particle technology, which can either be a dense
fluidized bed or an entrained bed.
(2) Effective Heat Transfer and Utilization. The
cracking reactor must be able to transfer heat to the re-
action at temperatures of 500-550 OC. Cracking generates
large amounts of coke, and the heat of combustion must
be removed in a controllable way while utilizing the heat
 Ind. Emg. Chem. Res., Vol. 29, No. 6, 1990 937
of combustion efficiency. In principle, one can use most PRODUCT

of the heat of combustion for steam generation and power

recovery and supply the heat of cracking separately. But
complete thermal independence between reactor and re-
generator not only complexes the design but also lowers
the overall thermal efficiency. It is more efficient to utilize
a large part of the heat of combustion in a direct way. This
has lead to the "heat-balanced" concept in FCC where the
catalyst particles carry sensitive heat to vaporize, preheat,
and supply the heat of cracking. Part of the heat of com-
bustion is recovered from the flue gas, and part is lost. The I-STOCK

FCC unit is heat integrated on the reactor side as well, and CHARGE
the feed in preheated by heat exchange with products. STOCK
PREHEATER
Other heat-exchange means, such as fired feed preheater,
and an external cooler to remove heat from the regenerator FLOW SHEET, HOUNDRY PROCESS

are also used to provide flexibility and controllability. Figure 14. Schematic diagram of the fixed-bed catalytic cracking
The regenerator is not always in balance with the heat unit.
requirements of the reactor. It is therefore desirable to A~xAIR AND OIL VAPOR OUTLET
design the system so that heat can be both added and
removed independently. The regenerator itself should be I

operated as closely to isothermal conditions as possible. CATALYST FILLER PIPES

This requires efficient heat removal. If combustion rates
are fast due to high temperatures, the catalyst particles
have to be small to avoid excess temperatures due to
TOP TUBE SHEET- AI I/
diffusional limitation inside the particles. Heat can be
removed in two ways: by heat exchange inside the com-
bustion zone, using either water, molten salt, or molten
metals, or by using catalyst flow to remove heat from the
regenerator to the cracking reactor. 77m
Fluidized bed technology has a large advantage in heat
removal. Fluidized beds have intense mixing of the solids REGENERATIO
and therefore high heat-transfer coefficients and close to .5m

isothermal operation. In a tubular reactor, the temperature CATALYSTTUBE SHEET

nonuniformity in the catalyst bed is a function of diameter, I l l

VAPOR HEADER

Tm
local flow rate, and local reaction rates. This puts strong
limitations on the maximum allowable local reaction rates. MAIN TUBE SHEET
The requirements of efficient heat removal and heat ad-
lm
dition are often the dominating parameters in the choice
SALT OUTLETS
of the reactor.
The heat-transfer requirement, together with the re-
quirement of catalyst reactivation, dominated the devel-
opment of hardware and catalyst technologies. The de-
signs that were developed in the past 50 years form the
basis for many other present reactor designs. VAPOR TUBES-
(55)
(3) Operating at High Temperatures. Operation at LEGEND
a
higher temperatures only became desirable for high-ac-
tivity catalysts that were not available at the time of
AIR OR VAPOR PATHS
SALT PATHS
0CATALYSTSPACE
L L SOIL
AIR AND A LVAPOR
T i N INLET
L E T

different designs developed. Short residence times are
possible in fixed beds, but short residence times at high
temperatures require very rapid heating of the feed. If the
heating of the feed is done by hot catalyst particles, then
the temperature of the particles is significantly higher than
the averge cracking temperature. Mixing must be rapid
to avoid thermal cracking. This strongly limits the particle
size, as the heating time of 3-mm particles is about 2 s.
(4) Operating with Changing Feed and Changing
Product Requirements. Cracking feedstocks can vary
widely, and the cracker must be able to handle a wide
variety of feedstocks. Product demands vary seasonally.
Modern fluidized bed crackers are able to meet these de-
mands by changing catalyst type or activity, reaction
temperature, and space velocity.
Changing feed properties and conversion also affects the
heat balance, as coke make and heat requirements of the
reaction change. In the next sections we will discuss how
different designs dealt with these issues.
11. Fixed-Bed Reactor
The first commercial catalytic cracking reactor was a
NOTE DRAWING IS NOT TO SCALE DISTANCES ARE APPROXIMATE ONLY A FEW TUBES ARE
SHOWN FOR THE PURPOSE OF FOLLOWING THE OIL FLOW SMALL ARROWS INDICATE
PATH OF AIR AND OIL VAPORS THRU THE CASE
Figure 15. Diagramatic sketch of commercial Houdry case.
fixed bed (Figure 14). It was jointly developed by Eugene
Houdry, Sun Oil, and Socony Vacuum, the forerunner of
Mobil. The first 2000-BPD unit was started up in April
1936 in the Paulsboro, NJ, refinery. Its reactors contained
acid-treated natural clay catalyst. Three reactors were
operated in parallel, and they were switched from cracking
to regeneration every few minutes. The heat transmission
between cracking and regeneration was achieved by a
molten salt heat exchanger. The molten salt was flowing
through the reactor in a series of tubes that were equipped
with fins to increase heat transfer (Figures 15 and 16).
The molten salt extracted the heat from the reactor op-
erating in the combustion mode and transferred it to the
reactor operating in the cracking mode.
The fixed-bed reactor was an ingenious solution to meet
the requirements of a cracking reactor with the technology
available then. It represented a major milestone in process
technology, including such highlights as the first wide-
938 Ind. Eng. Chem. Res., Vol. 29, No. 6, 1990
TUBE SIZES AIR
1. REGENERATIONTUBES - OUTSIDETUBE - Scm.
INSIDETUBE - 3cm.
2. DISTRIBUTORTUBES - OUTSIDETUBE - 6cm.
INSIDETUBE - 3cm.
TO REACTOR
3. COOLINGTUBES - OUTSIDETUBE - 6cm.
INSIDETUBE - 3cm. /
STEAM I
4. COOLINGTUBES - 3.3cm.

HEATCONDUCTING FN
I S- TUBE

TlON

I ELEVATOR
VESSEL
BLOWER
THERMOCOUPLE 1 AND OIL VAPORS
ARRANGEMENT t ENTER CATALYST BE13 Figure 18. Schematic diagram of the TCC air lift process.
u
(AIR AND OIL VAPORS LEAVE CATALYST BED
The other requirements listed in section 10, namely
THROUGH COLLECTOR TUBE ORIFICES)
operating at high temperatures and short residence times,
NOTE DRAWING IS NOT TO SCALE and the ability to handle a large variety of feeds, were not
Figure 16. Cross-section sketch of typical tube unit layout for as important in the late 1930s. The two competing
commercial Houdry case. cracking technologies were developed to improve on item
1, the ability to handle a fast-changing catalyst.
Instantaneous Yield Today's salt-bath tubular reactors are descendants of
50 this technology, and in practically all of them, the catalyst

Gasoline
Yield, r-11 1
45
is contained in tubes. Most of them operate with long
times between regeneration (2 weeks to a year). There is
no need to utilize the heat evolved in the regeneration.
Only one major process still operates with very frequent
I-
40 \\ I switching between reaction and regeneration-catalytic

35t
30
\\ I Amorphous Catalyst

I I I \\
60 70 80 90
Figure 17. Integrated gasoline yield in a fixed-bed reactor vs in-
stantaneous yield achievable in a constant activity reactor (based on
FCC kinetic model (Jacob et al., 1976)).
spread use of catalysis in petroleum refining, air regen-
eration of coked catalysts, and the implementation of au-
tomatic process control. however, considering the demands
of the cracking reactor given in section 10, the fixed-bed
reactor had shortcomings.
(1)Fractions of feed saw an increasingly deactivated
catalyst. The first fraction was overcracked, whereas the
last fraction had low conversion. This is similar to a re-
actor with a broad residence time distribution. Conversion
is integrated over different histories, which reduces in-
termediate yields in consecutive reaction schemes. This
is illustrated in Figure 17, where the integrated yield is
compared to the instantaneous yield.
If catalyst deactivation is slow, one can compensate for
it by raising the temperature. This is impractical in cat-
alytic cracking, as deactivation is too fast and the tem-
perature is already high. The large thermal holdup of the
salt bath would not allow such a control scheme. This
would be possible if the time scale of the deactivation was
measured in weeks instead of minutes.
(2) Temperature distribution was not uniform during
combustion, thus limiting the maximal regeneration tem-
perature.
I
dehydrogenation of butane and propane (Catofin and
Cadadiene). This reactor is a direct descendant of the
Houdry reactor, but also has moving bed and fluid-bed
competitors. The moving bed process, UOP's Oleflex, has
100
been introduced recently. It is based on the moving bed
CCR reformer, which in turn is based on TCC principles.
Fluid-bed technology has been practiced in the Soviet
Union and Romania.
12. Moving Bed Reactor (TCC)
A schematic representation of a TCC unit is given in
Figure 18. The moving bed reactor uses large catalyst
particles (3-5-mm spheres). The catalyst moves by gravity
from the reactor section to the regenerator section, and
the regenerated hot catalyst is lifted by an airlift to a
solids-air separator from which the catalyst is fed by
gravity to the reactor. A small side stream is fed to an
elutriator to remove fines generated by attrition.
The TCC had many advantages over the fixed-bed re-
actor and allowed much larger units. It solved one of the
major problems of the Houdry reactor, namely, constantly
changing catalyst activity. The mechanical problems of
such a system were formidable but were solved by elegant
design. This technology has found important new uses
such as in UOP's continuous catalytic reformer (CCR) and
Oleflex processes.
While the TCC had large advantages over the fixed-bed
reactor, it still fell short in meeting the requirements given
in section 10. The large particle size limited the regen-
erator temperature to below 650 "C, requiring a large re-
generator and large catalyst holdup (Prater et al., 1983).
 Ind. Eng. Chem. Res., Vol. 29, No.6, 1990 939
1.o 1.o

Per Typical Gas Velocities

for Fine Powders (mh):

lh Bubbling 0.1
Turbulent 0.5
Fast 3 -
-
.
0.1

Riser 10 - Solid
Volume 0.01
Height 0.5
Fraction
Non-Dimentional
Turbulent
0.001

Bubbling

0 I \ I I -___
n.ow1
0 0.2 0.4 0.6 0.8 0.001 0.01 0.1 10 10 100
Solid Volume Fraction Superficial Gas Velocity ( mis)

Figure 19. Axial density profiles in fluid beds. Figure 20. Modern high-efficiency FCCU with riser reactor and
riser regenerator-fluidization regimes (from Squires et al. (1985)).
(Modern TCC catalysts allow regenerator temperatures of FLUE GAS
up to 675 "C, in properly designed kilns.) Furthermore, VENT REGENERATED

it was difficult to transfer the heat of combustion to the

reaction zone. Due to the large particle size, the difference
in temperature between the reactor and the regenerator
had to be minimized. The required difference is a function
of catalyst to oil (C/O) ratio. In early (bucket elevator)
TCC units, this ratio was limited to 1.5, the air-lift TCC
reached 4.5, and the later designs reached a value of 7.
C/O ratios of 9 or more are possible in FCC units.
This meant that the TCC regenerator had to be cooled
by steam generation, and the feed had to be vaporized.
Later TCC designs would accept liquid feed but still re-
quire a high preheat of a t least 400 "C. TCC reactor
temperature was typically 500 "C and could be raised up MODEL I SCHEMATIC
to 525 "C. On the positive side, the moving bed with a
vapor feed has very uniform contact time distribution Figure 21. Schematic diagram of the upflow model I FCCU (1942).
(provided that reaction rates are low enough so that par-
ticle diffusion is not controlling). PRODUCTS
A moving bed design falls short a t meeting the re- 4 TO SEPARATION TOWER

quirements of high temperatures, short residence times,

and changing feed properties. The large particle size limits
the rates of heat and mass transfer. The large catalyst
holdup increases the response time of the system to cat-
alyst changes, which limits the ability of the cracker to DISTRIBUTION GRID
handle variations in feedstocks and product demands.
These shortcomings were not as important 50 years ago ONTROL STEAM
as they are today. There were no active catalysts to allow
high temperature and short residence times. PREHEAT FURNACE

Another disadvantage of TCC technology was not re- YCLE

lated to reaction engineering but to mechanical design

problems. The cost of most process equipment per unit
feed decreases with increasing capacity. However, for each
unit there is a critical size at which the cost per unit starts
to increase with size. For a TCC this happens a t about
30000 BPD. FCC's have strong cost advantages for larger
sizes. The average size of an FCC unit has increased over
the years to about 40000 BPD, and units as large as
130OOO BPD have been constructed.
13. Fluid-Bed Reactor (FCC)
An alternative way to realize the flow scheme shown in
Figure 13 is to use fluid-bed technology. FCC catalyst
consists of spherical particles, with a particle size varying
from 1to 130 Fm. When a fluid is passed through a bed
of solids, the pressure drop increases, and when it exceeds
bed weight, the solids start to mix and behave like a fluid.
At higher velocities, bubbles form and then undergo con-
tinuous breakup and coalescence until the bed reaches the
turbulent fluidization regime. As gas velocity is raised
further, the boundary between bed top and freeboard
disappears and the entrainment rate increases. The fluid
bed is maintained by feeding back the entrained particles.
RESIDUE
Figure 22. Schematic diagram of the Model IV FCCU (1952).
Typical axial density profiles are shown as a function
of gas velocity in Figure 19. It should be noted that there
is a transition between a dense turbulent bed to a more
dilute entrained bed. There is a gradual increase in top
density and a decrease in bottom density. Most academic
research has concentrated on bubbling beds, whereas most
commercial interest has been in "bubbleless" fluidization
(Squires et al., 1985). The high-velocity, bubbleless regimes
are used for cracking and regeneration, as shown for a
modern high-efficiency FCC unit (Figure 20).
Fluid beds have certain advantages over moving beds.
(a) They can handle smaller catalyst particles.
(b) Solid circulation rates can be adjusted over a wider
range.
(c) Fluids and solids can be mixed quickly, and rapid
solids movement greatly improves heat transfer.
An early FCC design is shown in Figure 21, which gives
a schematic representation of the first Easo Model I upflow
940 Ind. Eng. Chem. Res., Vol. 29, No. 6: 1990
design (1942), and the 1952 vintage Model IV is shown in
Figure 22. Model I was an “upflow” system, while Model
IV was a “pressure-balanced downflow” system. Model I,
which was the first commercial fluid-bed system using a
fine powder, had many advanced features that were
dropped in later models but eventually were reintroduced.
It had upflow cracking and regeneration, quick separation
of cracked products from spent catalyst, and catalyst
coolers and feed preheat (”non-heat-danced” operation).
Model I and most later FCC designs (except for Model IV)
share some basic features: Catalyst flow rates can be ad-
justed over a wide range, allowing for great flexibility in
opertion.
In this paper we are not concerned with a detailed
discussion of the design changes that led to todays different
FCC units, but rather in the way the demands outlined
in section 10 effected the design. Let us start with the
regenerator
14. FCC Regenerators
Early FCC regenerators operated at tempertures below
650 “C. At these temperatures, there was little CO com-
bustion in the gas phase. The flue gas ignited once the
solids were removed from the gas in the cyclone due to the
presence of CO and oxygen, and the absence of solids that
quench free radicals. This afterburning could lead to ex-
cessively high temperatures in the cyclones, and oxygen
conversion needs to be high, leaving less than 0.2% oxygen
in the flue gas. Such high conversions are difficult to
achieve in low-velocity fluid beds without a catalytic
combustion promoter (if low carbon level on regenerated
catalyst is desired). There is significant bypassing in a
large bubbling bed, especially in shallow regenerator beds
that were designed to minimize pressure drop and air
blower costs. The practice of operating with low fines
concentrations (because of low efficiency cyclones) caused
large bubbles and aggravated the problem.
Fluid-bed regenerator efficiency can be improved by
operating at higher velocities such that there is a significant
catalyst concentration in the freeboard. A typical FCC
regenerator operates in turbulent fluidization at a gas
velocity of 1 m/s, such that about 20% of the catalyst is
in the freeboard. In fact, whole bed circulates through the
cyclones about every 5 min. This solids holdup in the
freeboard allows relatively high conversions in these
shallow, inefficient regenerators. However, afterburning
in the cyclones can still be a problem. The temperature
rise due to afterburning is used to control the regenerator.
To achieve higher CO conversion, one needs to provide
combustion to COz either by raising the temperature
(above 700 “C) or by utilizing a catalytic combustion
promoter. Small amounts of Pt allow complete CO con-
version at temperatures of 650 “C. The activation energy
of CO combustion with a catalyst is only 20 kcal/mol
(Prater et al., 1983).
Even early FCC regenerators benefited from nearly
isothermal conditions. Hot spots, which can easily develop
in fixed-bed or moving bed reactors (there is no lateral
mixing in TCC), are eliminated in fluidized beds. For the
same reason, fluid-bed chemical reactors (such as acrylo-
nitrile) can be operated in the explosive regime, without
ever exploding. Still, fluid bed reactors are not completely
isothermal. Lateral and vertical temperature differences
can reach 50 “C, and larger temperature fluctuations can
occur over very short time periods. But the impact is much
less than that of excess temperatures inside a large catalyst
particle.
FCC regenerators underwent many changes over the
years. One particularly successful design is the “high-
efficiency”regenerator shown in Figure 20. The turbulent
fluid bed at the bottom of the combustor is turned into
an entrained fast fluid bed by reducing the vessel diameter.
The solids are separated from the gas in an inertial sepa-
rator in the upper combustor. Part of the regenerated
catalyst is returned to the base of the riser reactor, and
part is recirculated to the lower combustor. This design
resulted in a smaller vessel and better gas-solids contact
inherent in high-velocity fluidization regimes. The high-
velocity regenerator is more forgiving toward initial dis-
tribution problenis and allows reduction in unit inventory.
It also allows complete CO combustion with little excess
air and little or no promoter.
Another new regenerator type uses two-stage combus-
tion. The fast-burning hydrogen-rich compounds are
combusted first at lower temperature in the first regen-
erator, and the slow-burning residual coke is combusted
at a high temperature in the second regenerator. This
concept has been commercialized in some resid cracking
FCCU’s. The goal of this design is to reduce the exposure
of the catalyst to steam generated in the combustion, as
the hydrogen content of the coke and therefore the steam
content in the flue gas are lower in the high-temperature
zone. The two-stage design reduces catalyst makeup and
increases the flexibility of the unit.
15. FCC Reactor
The Model I FCC reactor was an upflow pipe or riser,
with an expanded diameter section designed to provide
more residence time. The upflow mode is also used today
but at much shorter residence times. The designers of this
early fluid-bed system soon discovered that fine powders
do not seem to obey Stokes’ law. Even at velocities several
times higher the single-particle terminal velocity (which
is approximately 0.1 m/s for FCC catalyst), the bed is not
entrained immediately. The particles behave as clusters
with an effectively higher terminal velocity due to inter-
particle forces. This realization led to the development
of Model I1 and subsequent “downflow”fluid-bed reactors.
The expanded reactor section was elongated, a dense fluid
bed was formed, and the solids were withdrawn from the
bottoms, rather the top of the bed. The higher bed density
in these downflow system allowed long contact times and
lowered catalyst losses which were high in Model I.
Improvements in catalysts, brought about by introduc-
tion of synthetic silica-alumina to replace natural clays,
followed by high alumina catalysts, caused more of the
cracking reaction to occur in the riser leading to the re-
actor. Mobil’s invention of zeolite-containing cracking
catalysts in the early 1960s has eliminated the need for the
dense bed altogether. Existing FCC reactors were modified
to all riser cracking, usually by extending the riser through
the reactor vessel. The “reactor”vessel, which is still called
reactor in many installations, now houses the riser cyclones
and, in some designs, the catalyst stripper (which uses
steam to remove some adsorbed hydrocarbon from spent
catalyst).
The modern FCC reactor is different from conventional
catalytic fluid-bed reactors. The catalyst is introduced
through a standpipe, and oil feed is introduced into the
bottom of the riser section. This allows rapid mixing be-
tween the vaporizing feed and hot regenerated catalyst.
The bottom of the riser is a complex environment. There
are strong axial and radial temperatures and solid con-
centration profiles. The desired goals for the mixing zone
are rapid mixing of solids and oil and minimizing catalyst
holdup in the zone. A high catalyst holdup indicates that
vaporization is slow and that, therefore, the oil residence
time is larger than indicated by average gas velocity.

b) Time-Temperature Regimes for Fluid-Solids Systems
2000 r QC Reaction
Temp.,lmE
‘F
Art
500 I I
0.1 1.0
Residence Time, Sec.
1
SolldS
Figure 23. QC reaction system (from Gartside (1989)).
Reactor design in modern FCC units still falls short of
the goals outlined in section 10. The achievable residence
time is still larger than desired to achieve the optimum
ratio of chemical to catalytic cracking at high temperatures.
The limitations are in the gas-solids separation as well as
in the bottom mixing zone. Recent advances in quick
gas-solids separation have moved the main constraint into
the bottom mixing zone. Vaporization and cracking re-
quire milliseconds for an active catalyst, but it is difficult
to mix large amounts of catalyst (over 60 tons/min in a
large unit) with cold oil feed within milliseconds. There
is therefore a strong variation in the temperature-time
activity history that different elements of the feed undergo.
In that sense, the effective contact time distribution is
highly nonuniform. One can measure the impact of this
nonuniformity by comparing the overall results with that
of a small pilot plant. The differences are important
enough to merit improvement, but they are not large
enough to outweigh the other advantges of this design.
Faster mixing and shorter residence times are still an
area where there is still a place for novel designs. One
interesting development is the “quick contact” (QC) system
described in Figure 23. This sytem can contact feed and
catalyst, react them, and separate and quench them in less
than half a second. (Current systems need more than 1
s.) However, no commercial plants are yet in operation.
Understandingand modeling highly nonisothermal mixing
systems in which residence times and mixing times are of
comparable magnitude is still a challenge for the reaction
engineer.
There is another interesting lesson for the reaction en-
gineer. The conditions at the bottom zone of a modern
FCC riser are far beyond our capabilities to realize detailed
scaleup by predictive modeling. This was less severe a
problem in earlier designs as catalysts were less active and
temperature differences were much smaller. We have to
realize that sometimes successful designs involve risks.
Such risks can be minimized but not avoided.
16. Design for Controllability
One important consideration in the choice and design
of a reactor is the ability to control it (Shinnar, 1981; Lee
and Weekman 1976). In a reactor that has the potential
for multiple steady states, it is also important that the
dynamic control be able to maintain unconditional as-
ymptotic stability. In addition, the cracker has to handle
a wide variety of feedstocks and to change the product
distributions and product specification, upon short notice.
FCC’s ability to accept a wide range of feedstocks makes
it the kingpin in controlling the whole refinery. Changing
FCC operating conditions allows changes in the ratio
gasoline to heating oil, when demands change from winter
Ind. Eng. Chem. Res., Vol. 29, No. 6, 1990 941
Major Control Loops
(Other Loops Omitted for Clarity)
Regenerator Reactor
UJ I-- To Main
Fractionator
A-P
+
(P+ I D)
Set
I I .
10 100
Generation
Air
Furnace
Oil Fuel
Figure 24. One FCC control scheme with steam generation in the
regenerator (Shinnar, 1981).
to summer. It also allows trade-offs between gasoline yield
and octane. The fluid-bed unit has a greater degree of
flexibility than both the fixed-bed and moving bed reac-
tors. The degree of flexibility is a strong function of design
and varies strongly in different designs. The critical items
which allow FCC to operate over a wide range of conditions
are as follows.
(a) Catalyst. Continuous (or daily) catalyst addition
and withdrawal of equilibrium catalyst compensate for
permanent deactivation. The catalyst change in FCC is
much more rapid than in TCC due to the lower inventory.
The whole inventory in FCC is typically replaced every
50-100 days, and response to a new catalyst or additive
is much quicker.
(b) Reactor Temperature. Temperture is an inde-
pendent variable that adjusts steady-state catalyst activity
and allows changing product slate and properties (such as
gasoline octane).
(c) Catalyst Circulation Rate. Catalyst circulation
rate can be adjusted over a wide range in most FCC de-
signs. In a truly adiabatic FCC, in which there is no feed
preheat and no catalyst cooler, the circulation rate for a
given reaction temperature is mainly a function of regen-
eration temperature and therefore strongly constrained.
If a preheat furnace is added to the unit, the catalyst
circulation rate can be adjusted over a much wider range.
Catalyst coolers are also used to adjust FCC heat balance.
Catalyst type also affects circulation rate. A coke-selective,
ultrastable catalyst would not change the coke yield in a
heat-balanced unit but would lower the carbon on spent
catalyst. The C/O ratio will hence increase.
(d) C 0 2 / C 0 Ratio. Another important factor im-
pacting the heat balance is the C02/C0 ratio in the re-
generator. If no combustion promoter is used, this ratio
is solely a function of regenerator temperature. Pt pro-
moter allows operation at full CO combustion, at any op-
erating temperature in most units. If one desires to operate
at partial combustion, a CO boiler is needed to complete
the combustion of the flue gas. Use of a promoter allows
fine tuning of this ratio and thereby control of the heat
balance.
These and other control items are combined into an
overall control scheme, such as the one shown in Figure
24 (Shinnar, 1981). The two main variables that would
affect the conversion are reactor riser top temperature,
which controls the catalyst circulation rate, and feed
preheat temperature. One important control variable,
available in the first Model I FCC unit and recently res-
942 Ind. Eng. Chem. Res., Vol. 29,No. 6,1990
urrected, is heat removal from the regenerator. Steam is
generated in coils or an external catalyst cooler. This
arrangement is especially useful when processing heavy
feeds, such as resids with high CCR levels.
Modern FCC design meets most of the criteria outlined
in section 10 well and definitely meets most of those
criteria better than any of the other designs. There are
still two areas in which FCC designs fall short.
(1)The lower limit of residence time is still higher than
desirable, mainly due to limitation of the bottom section
and the gas catalyst separation.
(2) The contact time distribution is not uniform. Fur-
thermore, the temperature activity history of different fluid
elements can vary considerably.
These shortcomings still leave room for future imagi-
native design. But any design is a compromise, and the
present designs are better compromises than former
technologies. We hope that the previous discussion is
useful for the student in reaction engineering in teaching
him that reactor design has to take into account a large
variety of factors and always involves compromises.
Acknowledgment
The figures in this paper are intended to demonstrate
trends rather than show exact data. We are grateful to
Raymond Hu for his assistance with Figures 1 , 2 , 7 , 8 , 11,
12, and 16. Lee Breckenridge supplied us with Figure 5.
Figures 4 and 6 are drawn after several authors, including
Voorhies; orders of magnitude was taken from Mobil re-
searchers Farber, Payne, and Sailor (1965). Most other
figures are adapted from Avidan et al. (1990).
Nomenclature
A = constant in Voorhies equation (0.2-0.9 in ref)
Aj, = constant determined by feed
C = coke yield, wt % of feed
C, = carbon deposited on catalyst, wt 70 (carbon on spent
carbon on regenerated catalyst)
CCR = Conradson carbon residue, or continuous catalyst
regeneration (when applied to reforming)
Cj= outlet reactor composition (eq 16)
C/O = catalyst to oil weight ratio
FCC = fluid catalytic cracking
H/C = hydrogen to carbon atomic ratio in coke
I&EC = Industrial & Engineering Chemistry
k, = coke yield divided by crackability, X
kj = catalyst activity for each reaction shown in eq 8
k,, kj, = catalyst activity for regenerated catalyst
n = Voorhies exponent, about 0.5 in Voorhies’ work
Ri = rate matrix for first-order reaction network (eq 15)
t , = catalyst residence time, min
TCC = thermofor catalytic cracking
WHSV = weight hourly space velocity
X = conversion (=lo0- vol % yield of products heavier than
gasoline, typically above 220 OC)
X = Crackability, (=X/(1- X))
AG = change in Gibbs free energy
AH = change in enthalpy
@ = catalyst deactivation function
A, = eigenvalues of the rate matrix Ri
T = time constant related to WHSV in eq 16
‘;k(t)= contact time distribution
*(t) = Laplace transform of Jr(t)
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Received for review October 6, 1989
Revised manuscript received January 18, 1990
Accepted February 22, 1990